Liquid suspension of high density particles



tates Hoyt H. Todd, Whittier, Calif.

No Drawing. Application June 20, 1955 Serial No. 516,781

3 Claims. (Cl. 106-290) This invention relates to suspensions of high density particles of greater than colloidal size in a liquid medium and further relates to methods for increasing the stability of such suspensions.

By high density particles is meant particles having a specific gravity at least on the order of magnitude of 2.25. When such particles are uniformly suspended in a liquid medium of substantially less specific gravity and is allowed to stand, the particles will inevitably settle to the bottom of the liquid and after a period of time, which may be conveniently termed the settling time, the mixture will divide into two readily differentiated parts, namely, a lower sedimentation part, and an upper part of more or less clear liquid. The stability of a liquid suspension may be measured by the duration of this settling time.

The present invention increases the stability of a suspension of high density particles of greater than colloidal size. In some instances, the settling period is so greatly prolonged that the suspension may stand for several months without observable change from its initial homogenous appearance. In other instances, the increased settling period will be much shorter. Stability is a relative matter both in the sense that a suspension having a settling period of days is stable in comparison to a suspension having a settling period of only 5 days, and in the sense that a suspension having a settling period of 5 days is stable from a practical standpoint if each batch of the suspension is always consumed in a lesser period of time.

The invention is based on the following underlying principles and discoveries:

(1) The tendency for high density particles to settle in a liquid medium of substantially lower density under static conditions may be greatly reduced by attaching gas bubbles to the particles to form particle-bubble units of approximately the same specific gravity as the liquid medium. In practice the specific gravity of each and every particle-bubble unit will not exactly match the specific gravity of the liquid medium, but the median specific gravity of the particle-bubble units may be brought approximately to the specific gravity of the liquid medium, or at least close enough for the purpose of the invention.

(2) Increasing the viscosity of the liquid medium retards the rates of rise and fall of the particle-bubble units in the liquid medium in response to specific gravity differentials.

(3) With exercise of due care to avoid an excessively wide range of particle size distribution, as well as bubble size distribution, the range of specific gravity differentials may be narrowed to such an extent that merely selecting a liquid medium of substantial viscosity reduces the rates of gravity-induced movements of the particle-bubble units to such extent as to make the separation effect of such movements insignificant if not incompletely imperceptible over relatively long periods of static storage. Various substances may be added, if necessary, to raise the vis- 2,854,346 Patented Sept. 30, 1958 cosity of a low-viscosity liquid medium to the required degree. These first three points may be understood when it is considered that the rate of gravity-induced movement in a liquid of spherical solid particles of greater than colloidal size varies in accord with in which:

D =density of the spherical particles. D density of the liquid medium. Rzradius of the spherical particles. V=viscosity of the liquid medium.

(4) Gas bubbles may be caused to adhere to high density particles or metallic particles in a liquid by coating the particles with a substance that is more adherent or wettable by a gas than by a liquid. The amount of gas to be introduced into the liquid medium for adherence to the coated particles is rather critical but in practice is readily ascertainable by a person skilled in the art. In general, the amount of gas to be used for satisfactory results varies inversely as the size of the particles and varies directly with the density of the particles and with the concentration of the particles in the liquid medium. The introduction of too great a quantity of gas into the system will destroy the stability of the suspension. If the bubbles attached to the coated particles become too large, the bubbles coalesce to form large bubbles that rise to the surface of the suspension. This action releases the gas and makes the suspension unstable.

(5) Some coating substances may be added to the liquid medium to coat particles therein; other coating substances may be applied to the particles prior to immersion of the particles in the liquid. In the presently preferred practice of the invention, the coating is applied to the particles prior to immersion and the coating material must not be of such character as to cause the particles to adhere together in clusters. Coating materials suitable for the purpose of the invention include, for example, oleic acid, palmitic acid, stearic acid, sodium salts of these acids, sodium ethyl xanthate, n-amyl mercaptan, amyldisulphide, dicresyl phosphates, and hydrocarbon oils. Such materials are commonly termed collectors" in the mineral dressing art.

(6) The introduction of the gas into the liquid medium may be accomplished in some instances by agitation, for example, by beating or rapidly stirring the liquid.

(7) In some instances the gas for adherence to the coated particles may be provided by introducing a liquid supersaturated with a gas. Carbonated water or water aerated under pressure may be used for this purpose.

(8) The required gas may be provided in the liquid medium by using a water soluble chemical substance that will decompose in the liquid to create a gas. Hydrogen peroxide is suitable for this purpose in an aqueous liquid medium since its decomposition product is pure water: 21-1 0 9 2H O+O If the high density particles are finelv divided metal, the hydrogen peroxide decomposes catalvtically at the surface of the particles with no assistance from other chemical agents.

(9) The required gas in the liquid medium for adherence to the particles may be provided by the interaction of an acid and a base. For example, the liquid medium may be made slightly acidic and calcium carbonate may be introduced into the acidic medium to interact therewith for the release of carbon dioxide.

(10) In some instances the required gas may be provided in the liquid medium by employing a liquid medium having an adequate quantity of gas dissolved therein, and

then heating the liquid medium to drive the gas out of solution.

(11) In some instances a liquid medium may be employed with gas dissolved therein and the gas may be released to form the required bubbles simply by applying a vacuum to the liquid.

('12) Various substances may be added to increase the viscosity of liquid media for the purpose of the invention, and the selection of such substances is within the skill expected of persons working in this art. For raising the viscosity of aqueous solutions such substances as gum tragacanth, gum cellulose, gum arabic, dextrin, and the like, may be added. Sodium carboxymethylcellulose is an inexpensive and efiective, stabilizer for solutions in which the pH is neutral or on the alkaline side, but I have found that this substance decomposes in solutions of pH below 7. Gum tragacanth, gum arabic, andv dcxtrin are stable over a pH range of approximately 2 to 10. Where a great increase in viscosity by the addition of only a small amount of substance is required in a neutral or alkaline liquid medium, sodium carboxymethylcellulose is recommended. Some high viscosity types of sodium carboxymethylcellulose give extremely high viscosity when added to a liquid in very small relative amount.

('13) The ratio of the liquid medium to the high density particles suspended therein may be reduced for some purposes to give the suspension a consistency of a paste. As will be explained, such a paste, for example, may be formulated for use in bonding metal parts by furnace brazing. A suitable lubricant may be added to such a The result is a stable paste that may be kept stationary for as much as a month in& sealed container with little evidence of separation between the liquid medium and the suspended metal particles. The soap (sodium stearate) coats the copper particles to serve as a collector to make the copper particles more wettable by a gas than by a liquid. The hydrogen peroxide serves as a gas generator to produce the fine bubbles for adherence to the coated copper particles. The added sodium carboxymethylcellulose raises the viscosity of the solution to a level that makes the gravity-induced movements of the particle-bubble units negligible, the mineral oil lubripaste composition to facilitate the flow of the composition through small ducts and nozzles. A brazing composition incorporating a lubricant, for example, an appropriate quantity of mineral oil may be readily applied to metal joints by means of a squirt can, pressure gun, or the like. The mineral oil also increases the bond between the bubbles and the high density particles.

(14) When bubbles are caused to adhere to the high density particles to make particle-bubble units, in effect, the size of the particles is increased with consequent increase in the effective volume of the particles. This feature of increase in the effective size of the particles may be utilized to increase the stability of a suspension, and in some instances the result is a suspension that will be stable over an indefinitely extended period of time even though the effective density of the particle-bubble units is actually substantially greater than the density of the liquid medium. Such an unusually high degree of stability is achieved when the volume of the liquid medium is just sufiicient to fill the voids in the mass of particlebubble units when that mass has had ample opportunity to settle. In practice such a stable suspension is accomplished merely by causing the bubble to adhere to the high density particle to result in the desired particlebubble units, then permitting the suspension to stand for the duration of its settling period, and finally carefully drawing off the excess liquid above the sedimentation level. It is apparent that in such a suspension the bubbles serve as means to space the high density particles apart in the liquid medium.

In one outstanding practice of the invention for the production of a copper paste to be used for furnace brazing, the following ingredients were mixed well together:

16 lbs. of copper powder.

80 grams of soap (sodium stearate).

24 grams of high viscosity sodium carboxymethylcellulose.

The following ingredients are then added and mixed well:

2450 cc. of water. 60, cc. of mineral oil. 16 cc. of 20 volume H 0 I for the dispersal of bubbles therein.

+ mesh 0.1max. -100+150 mesh 0.5 max. l50+200 mesh 4.0:max. -200+250 mesh 1.5max. 250+325 mesh 2.0-7.0 -325 mesh 90.0mm.

The sodium carboxymethylcellulose should have a viscosity, for example, on the order of magnitude of 1000 to 2800 centipoises in a solution of 1% concentration at 25 C.

Since. most of the substances that may be added to increase the viscosity of a liquid are susceptible to attack by molds and bacteria, it is necessary to add a small quantity of germicide to prevent decomposition of the suspension. The selection of such germicides is within the. skill expected in. this art. It has been found, for example, that 1% of pine oil or of formaldehyde will serve this purpose. If the high density particles are copper or silver no germicide is necessary since the metals themselves act as efficient germicidal agents.

The principle of the invention may also be applied to the production. of a relatively stable suspension of high density particles. in non-aqueous solutions.

In a further practice of the invention, for example, 75 grams of copper powder sufiiciently fine to pass through 300 mesh screen was intimately mixed with 3 grams of ethyl cellulose and 75 cubic centimeters each of toluol and acetone were added to the mixture. 0.5 gram of sodium secondary butyl xanthate was added and then the sample was thoroughly shaken in a glass graduate. Over the next 48 hours the sample was shaken occasionally to completely dissolve the ethyl cellulose. After the ethyl cellulose was completely dissolved, the sample was thoroughly shaken for thorough inter-mixture and After 48 hours the sample still had an initial appearance of complete unifonmity. In. contrast, a second sample processed in the same manner but with butyl xanthate omitted had a settling period of 4 hours.

A further feature of the invention is that high density particles, for example, metallic particles, may be coated with a collector to make the particles more adherent or wettable by a gas than by a liquid, and that such a coated powder product may be sold as a dry composition for ultimate use in the production of such suspensions. Thus soap coated copper powder may be prepared and stored or sold for ultimate use in the production of the previously described copper paste for use in furnace brazing.

My description of selected practices of the invention, by way of example and to illustrate the principles involved, will suggest modifications, substitutions and other departures from my disclosure that properly lie within the spirit and scope of the appended claims.

I claim:

1. A metallic paint comprising: a liquid medium; finely divided metallic pigment particles of greater than colloidal size suspended in said medium; a coating on said particles of a collector making the particles more wettable by a gas than by said liquid medium; and gas bubbles adhering to the coatings of the particles to form particlebubble units of approximately the same specific gravity as the liquid medium.

2. In the manufacture of a metallic paint comprising finely divided pigment particles of greater than colloidal size suspended in a liquid vehicle, the improvement which consists in coating said particles with a collector to make the particles more wettable by a gas than a liquid; and introducing gaseous fluid into the liquid vehicle to pro vide gaseous bubbles for adhering to the coatings of the particles thereby to form particle-bubble units capable of remaining in suspension in the liquid vehicle for longer periods of time than the metal particles alone.

3. In the manufacture of a metallic paint comprising finely divided pigment particles of greater than colloidal size suspended in a liquid vehicle, the improvement which consists in coating said particles with a collector to make the particles more wettable by a gas than a liquid; and agitating the liquid vehicle to introduce air to cause small air bubbles to adhere to the coated particles to form particle-bubble units of less specific gravity than the particles alone thereby to retard the settling rate of the particles in the liquid vehicle.

References Cited in the file of this patent UNITED STATES PATENTS 1,288,350 Wiser Dec. 17, 1918 1,337,548 Edser Apr. 20, 1920 1,417,263 Lauckenbach May 23, 1922 1,946,077 Kautfmann Feb. 6, 1934 2,007,137 Abrams July 2, 1935 2,144,953 Ziehl Jan. 24, 1939 2,240,151 Wampner Apr. 29, 1941 2,508,501 Guilie May 23, 1950 2,587,266 Wray Feb. 26, 1952 2,593,008 Chappell Apr. 15, 1952 2,594,313 Klinker Apr. 29, 1952 FOREIGN PATENTS 21,490 Australia Feb. 23, 1935 

1. A METALLIC PAINT COMPRISING: A LIQUID MEDIUM; FINELY DIVIDED METALLIC PIGMENT PARTICLES OF GREATER THAN COLLOIDAL SIZE SUSPENDED IN SAID MEDIUM; A COATING ON SAID PARTICLES OF A COLLECTOR MAKING THE PARTICLES MORE WETTABLE BY A GAS THAN BY SAID LIQUID MEDIUM; AND GAS BUBBLES ADHERING TO THE COATINGS OF THE PARTICLES TO FORM PARTICLEBUBBLE UNITS OF APPRROXIMATELY THE SAME SPECIFIC GRAVITY AS THE LIQUID MEDIUM. 